Crossed-beam Velocity Map Imaging Research Articles

Dynamics of carbene formation in the reaction of methane with the tantalum cation in the gas phase.

The controlled activation of methane has drawn significant attention throughout various disciplines over the last few decades. In gas-phase experiments, the use of model systems with reduced complexity compared to condensed-phase catalytic systems allows us to investigate the intrinsic reactivity of elementary reactions down to the atomic level. Methane is rather inert in chemical reactions, as the weakening or cleavage of a C-H bond is required to make use of methane as C1-building block. The simplest model system for transition-metal-based catalysts is a mono-atomic metal ion. Only a few atomic transition-metal cations activate methane at room temperature. One of the most efficient elements is tantalum, which forms a carbene and releases molecular hydrogen in the reaction with methane: Ta+ + CH4 → TaCH2+ + H2. The reaction takes place at room temperature due to efficient intersystem crossing from the quintet to the triplet surface, i.e., from the electronic ground state of the tantalum cation to the triplet ground state of the tantalum carbene. This multi-state reactivity is often seen for reactions involving transition-metal centres, but leads to their theoretical treatment being a challenge even today. Chemical reactions, or to be precise reactive collisions, are dynamic processes making their description even more of a challenge to experiment and theory alike. Experimental energy- and angle-differential cross sections allow us to probe the rearrangement of atoms during a reactive collision. By interpreting the scattering signatures, we gain insight into the atomistic mechanisms and can move beyond stationary descriptions. Here, we present a study combining collision energy dependent experimentally measured differential cross sections with ab initio calculations of the minimum energy pathway. Product ion velocity distributions were recorded using our crossed-beam velocity map imaging experiment dedicated to studying transition-metal ion molecule reactions. TaCH2+ velocity distributions reveal a significant degree of indirect dynamics. However, the scattering distributions also show signatures of rebound dynamics. We compare the present results to the oxygen transfer reaction between Ta+ and carbon dioxide, which we recently studied.

Imaging the Ion-Molecule Reaction Dynamics of O- + CD4.

While neutral reactions involved in methane oxidation have been intensively studied, much less information is known about the reaction dynamics of the oxygen radical anion with methane. Here, we study the scattering dynamics of this anion-molecule reaction using crossed-beam velocity map imaging with deuterated methane. Differential scattering cross sections for the deuterium abstraction channel have been determined at relative collision energies between 0.2 and 1.5 eV and ab initio calculations of the important stationary points along the reaction pathway have been performed. At lower collision energies, direct backscattering and indirect complex-mediated reaction dynamics are observed, whereas at higher energies, sideways deuterium stripping dominates the reaction. Above 0.7 eV collision energy, a suppressed cross section is observed at low product ion velocities, which is likely caused by the endoergic pathway of combined deuteron/deuterium transfer, forming heavy water. The measured product internal energy is attributed mainly to the low-lying deformation and out-of-plane bending vibrations of the methyl radical product. The results are compared with a previous crossed-beam result for the reaction of oxygen anions with nondeuterated ̧methane and with the related neutral-neutral reactions, showing similar dynamics and qualitative agreement.

Ta+ and Nb+ + CO2: intersystem crossing in ion-molecule reactions.

The reactions of Ta+ and Nb+ with CO2 proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta+ and Nb+, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta+ hinting at a bottleneck along the reaction path. The question on the nature of the bottleneck, whether it involves a crossing point or a transition state, could not be finally answered because theory located both close to each other. Here, we aim at shedding further light onto the impact of intersystem crossing on the reaction dynamics and ultimately the reactivity of transition metal ion reactions in the gas phase. We employ a combination of thermal kinetics for Ta+ and Nb+ with CO2 using a selected-ion flow tube (SIFT) apparatus and differential scattering cross sections for Nb+ + CO2 from crossed-beam velocity map imaging. The reaction with niobium again shows dominant indirect dynamics and in general very similar dynamics compared to Ta+ + CO2. At thermal energies, both reactions show sub-collisional rate constants with small negative temperature dependencies. Experiments are complemented by high level quantum chemical calculations of the minimum energy pathway. Statistical modelling well-reproduces the experimental thermal rate constants, and suggests that the Nb+ reaction is rate-limited by the intersystem crossing at thermal energies.

Reaction dynamics of S(3P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations.

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S(3P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C3H4S (loss of ethene or H2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Sulfur (3P) Reaction with Conjugated Dienes Gives Cyclization to Thiophenes under Single Collision Conditions.

We combine crossed-beam velocity map imaging with high-level ab initio/transition state theory modeling of the reaction of S(3P) with 1,3-butadiene and isoprene under single collision conditions. For the butadiene reaction, we detect both H and H2 loss from the initial adduct, and from reaction with isoprene, we see both H loss and methyl loss. Theoretical calculations confirm these arise following intersystem crossing to the singlet surface forming long-lived intermediates. For the butadiene reaction, these lose H2 to form thiophene as the dominant channel, H to form the detected 2H-thiophenyl radical, or ethene, giving thioketene. For isoprene, additional reaction products are suggested by theory, including the observed H and methyl loss radicals, but also methyl thiophene, thioformaldehyde, and thioketene. The results for S(3P) + 1,3-butadiene, showing direct cyclization to the aromatic product and yielding few bimolecular product channels, are in striking contrast to those for the analogous O(3P) reaction.

Imaging Frontside and Backside Attack in Radical Ion-Molecule Reactive Scattering.

We report on the reactive scattering of methyl iodide, CH3I, with atomic oxygen anions O-. This radical ion-molecule reaction can produce different ionic products depending on the angle of attack of the nucleophile O- on the target molecule. We present results on the backside and frontside attack of O- on CH3I, which can lead to I- and IO- products, respectively. We combine crossed-beam velocity map imaging with quantum chemical calculations to unravel the chemical reaction dynamics. Energy-dependent scattering experiments in the range of 0.3-2.0 eV relative collision energy revealed that three different reaction pathways can lead to I- products, making it the predominant observed product. Backside attack occurs via a hydrogen-bonded complex with observed indirect, forward, and sideways scattered iodide products. Halide abstraction via frontside attack produces IO-, which mainly shows isotropic and backward scattered products at low energies. IO- is observed to dissociate further to I- + O at a certain energy threshold and favors more direct dynamics at higher collision energies.

Dynamics of the Oxygen Atom Transfer Reaction between Carbon Dioxide and the Tantalum Cation.

The understanding of fundamental atomic-level processes often requires well-defined model systems. The oxygen atom transfer from CO2 to a transition metal cation in the gas phase presents such a model system. We investigate the reaction of Ta+ + CO2 for which the formation of TaO+ is highly efficient and attributed to multistate reactivity. Here, we study the atomistic dynamics of the oxygen atom transfer reaction by recording experimental energy and angle differential cross sections by crossed beam velocity map imaging supported by ab initio quantum chemical calculations. Product ion velocity distributions are dominated by signatures for indirect dynamics, despite the reaction being highly exothermic. Product kinetic energy distributions show little dependence on additional collision energy even with only four atoms involved, which hints at dynamical trapping behind a submerged barrier.

Imaging the Atomistic Dynamics of Single Proton Transfer and Combined Hydrogen/Proton Transfer in the O- + CH3I Reaction.

We report on reactive scattering studies of the proton transfer and combined hydrogen/proton transfer in the O- + CH3I reaction. We combine state-of-the-art crossed-beam velocity map imaging and quantum chemistry calculations to understand the dynamics for the formations of the CH2I- + OH and CHI- + H2O products. The experimental velocity- and angle-differential cross section show for both products and at all collision energies (between 0.3 and 2.0 eV) that the product ions are predominantly forward scattered. For the CHI- + H2O channel, the data show lower product velocities, indicative of higher internal excitation, than in the case of single proton transfer. Furthermore, our results suggest that the combined hydrogen/proton transfer proceeds via a two-step process: In the first step, O- abstracts one H atom to form OH-, and then the transient OH- removes an additional proton from CH2I to form the energetically stable H2O coproduct.

Imaging Reaction Dynamics of F-(H2O) and Cl-(H2O) with CH3I.

The dynamics of microhydrated nucleophilic substitution reactions have been studied using crossed beam velocity map imaging experiments and quasiclassical trajectory simulations at different collision energies between 0.3 and 2.6 eV. For F–(H2O) reacting with CH3I, a small fraction of hydrated product ions I–(H2O) is observed at low collision energies. This product, as well as the dominant I–, is formed predominantly through indirect reaction mechanisms. In contrast, a much smaller indirect fraction is determined for the unsolvated reaction. At the largest studied collision energies, the solvated reaction is found to also occur via a direct rebound mechanism. The measured product angular distributions exhibit an overall good agreement with the simulated angular distributions. Besides nucleophilic substitution, also ligand exchange reactions forming F–(CH3I) and, at high collision energies, proton transfer reactions are detected. The differential scattering images reveal that the Cl–(H2O) + CH3I reaction also proceeds predominantly via indirect reaction mechanisms.

Conservation of direct dynamics in sterically hindered SN2/E2 reactions.

Nucleophilic substitution (SN2) and base-induced elimination (E2), two indispensable reactions in organic synthesis, are commonly assumed to proceed under stereospecific conditions. Understanding the way in which the reactants pre-orient in these reactions, that is its stereodynamics, is essential in order to achieve a detailed atomistic picture and control over such processes. Using crossed beam velocity map imaging, we study the effect of steric hindrance in reactions of Cl- and CN- with increasingly methylated alkyl iodides by monitoring the product ion energy and scattering angle. For both attacking anions the rebound mechanism, indicative of a direct SN2 pathway, is found to contribute to the reaction at high relative collision energies despite being increasingly hindered. An additional forward scattering mechanism, ascribed to a direct E2 reaction, also contributes at these energies. Inspection of the product energy distributions confirms the direct and fast character of both mechanisms as opposed to an indirect reaction mechanism which leads to statistical energy redistribution in the reaction complex. This work demonstrates that nonstatistical dynamics and energetics govern SN2 and E2 pathways even in sterically hindered exchange reaction systems.

Reaction dynamics of Al + CO2 → AlO + CO studied by a crossed-beam velocity map imaging technique.

The oxidation reaction of a gas-phase aluminum atom by a carbon dioxide molecule was studied by employing a crossed-beam technique at two collision energies: 27.9 and 52.8 kJ/mol. A (1 + 1) resonance-enhanced multiphoton ionization via the D2Σ+-X2Σ+ transition of AlO was applied to ionize the product. For several rotational levels of AlO in the vibrational ground state, time-sliced ion images were measured for the first time, and the angular-kinetic energy distributions were determined. All angular distributions showed forward and backward peaks; the forward peaks were more pronounced than the backward ones at the two collision energies. The product kinetic energy showed rather narrow distributions whose peaks appeared at near to the highest limit estimated from the available energies. The rotational distributions of the counter product CO, derived from the kinetic energy distributions, suggested that only a limited number of rotational states were formed and that a small amount of energies go into this mode. These results suggested that the reaction proceeds via a short-lived intermediate in which the O-C-O keeps a nearly linear structure.

Not Available

The proton transfer reaction H3+ + CO is one of the cornerstone chemical processes in the interstellar medium. Here, the dynamics of this reaction have been investigated using crossed beam velocity map imaging. Formyl product cations are found to be predominantly scattered into the forward direction irrespective of the collision energy. In this process, a high amount of energy is transferred to internal product excitation. By fitting a sum of two distribution functions to the measured internal energy distributions, the product isomer ratio is extracted. A small HOC+ fraction is obtained at a collision energy of 1.8 eV, characterized by an upper limit of 24% with a confidence level of 84%. At lower collision energies, the data indicate purely HCO+ formation. Such low values are unexpected given the previously predicted efficient formation of both HCO+ and HOC+ isomers for thermal conditions. This is discussed in light of the direct reaction dynamics that are observed.

Imaging Proton Transfer and Dihalide Formation Pathways in Reactions of F(-) + CH3I.

Ion–molecule reactions of the type X– + CH3Y are commonly assumed to produce Y– through bimolecular nucleophilic substitution (SN2). Beyond this reaction, additional reaction products have been observed throughout the last decades and have been ascribed to different entrance channel geometries differing from the commonly assumed collinear approach. We have performed a crossed beam velocity map imaging experiment on the F– + CH3I reaction at different relative collision energies between 0.4 and 2.9 eV. We find three additional channels competing with nucleophilic substitution at high energies. Experimental branching ratios and angle- and energy differential cross sections are presented for each product channel. The proton transfer product CH2I– is the main reaction channel, which competes with nucleophilic substitution up to 2.9 eV relative collision energy. At this level, the second additional channel, the formation of IF– via halogen abstraction, becomes more efficient. In addition, we present the first evidence for an [FHI]− product ion. This [FHI]− product ion is present only for a narrow range of collision energies, indicating possible dissociation at high energies. All three products show a similar trend with respect to their velocity- and scattering angle distributions, with isotropic scattering and forward scattering of the product ions occurring at low and high energies, respectively. Reactions leading to all three reaction channels present a considerable amount of energy partitioning in product internal excitation. The internally excited fraction shows a collision energy dependence only for CH2I–. A similar trend is observed for the isoelectronic OH– + CH3I system. The comparison of our experimental data at 1.55 eV collision energy with a recent theoretical calculation for the same system shows a slightly higher fraction of internal excitation than predicted, which is, however, compatible within the experimental accuracy.

Isomer-specific product formation in the proton transfer reaction of HOCO+ with CO

The proton transfer reaction HOCO++CO → HCO+/HOC+ has been studied using crossed-beam velocity map imaging. Angular and energy differential cross sections were obtained for collision energies from 0.3 to 2.3 eV. Scattering in forward direction together with a prominent scattering angle-dependent internal excitation is found at all collision energies. The exothermic HCO+ product appears to be very dominant even at energies above the energy threshold for the formation of metastable HOC+ ion. To determine the HOC+ contribution for different angular ranges, a model has been developed. We obtain an upper limit for the HOC+ product isomer fraction of <2%. In theoretical calculations, we find the CO2-catalysed isomerisation channel to be energetically accessible. However, it may not have a strong impact on the isomer ratio. Chemical dynamics simulations are needed to shed more light on this question.

Excited state reaction dynamics of Ti(a⁵F(J)) + O₂ → TiO(A³Φ, B³Π, C³Δ) + O studied by a crossed-beam velocity map imaging technique.

Oxidation reactions of the gas-phase titanium atom in its excited state with oxygen molecule, Ti(a(5)F(J)) + O2 → TiO(A(3)Φ, B(3)Π, C(3)Δ) + O, were studied by a crossed-beam velocity map imaging technique at 14.3 kJ/mol of collision energy. Metastable excited Ti, Ti(a(5)FJ), was generated by an optical pumping method and the reaction products were detected by single photon-ionization followed by a time-of-flight mass analysis and a two dimensional detection. Three wavelengths were selected to ionize electronically excited TiO*, TiO(A(3)Φ, B(3)Π, C(3)Δ). Time sliced images were measured, and angular and speed distributions of TiO* were determined. In all three ionization wavelengths, the angular distributions showed a forward-backward symmetry with low intensity at the sideway direction. The speed distributions were represented by the distributions based on the statistical energy partition into products. These results suggested that the reaction of Ti(a(5)F(J)) to form TiO(B) and TiO(C) proceeds via a long-lived intermediate and confirmed that the mechanism proposed by the previous chemiluminescence study.

Reaction dynamics of Al + O₂ → AlO + O studied by a crossed-beam velocity map imaging technique: vib-rotational state selected angular-kinetic energy distribution.

Oxidation reaction of a gas-phase aluminum atom by a molecular oxygen was studied by a crossed-beam condition at 12.4 kJ/mol of collision energy. A (1+1) resonance-enhanced multiphoton ionization (REMPI) via the D(2)Σ(+)-X(2)Σ(+) transition of AlO was applied to ionize the product. The REMPI spectrum was analyzed to determine rotational state distributions for v = 0-2 of AlO. For several vib-rotational states of AlO, state selected angular and kinetic energy distributions were determined by a time-sliced ion imaging technique for the first time. Kinetic energy distributions were well represented by that taken into account initial energy spreads of collision energy and the population of the spin-orbit levels of the counter product O((3)P(J)) determined previously. All angular distributions showed forward and backward peaks, and the forward peaks were more pronounced than the backward one for the states of low internal energy. The backward peak intensity became comparable to the forward one for the states of high internal energy. These results and the rotational state distributions suggested that the reaction proceeds via an intermediate which has a lifetime comparable to or shorter than its rotational period.

Reaction dynamics of Mo + O2 → MoO + O studied by a crossed-beam velocity map imaging technique

The oxidation reaction dynamics of gas-phase molybdenum atoms by oxygen molecules was studied under a crossed-beam condition. The product MoO was detected by a time-of-flight mass spectrometer combined with laser multi-photon ionization. An acceleration lens system designed for the ion-velocity mapping condition, a two-dimensional (2D) detector, and a time-slicing technique were used to obtain the velocity and angular distributions of the products at three collision energies: 10.0, 17.8, and 50.0 kJ/mol. The angular distributions showed forward and backward peaks, whose relative intensities changed by the collision energy. While two peaks had similar intensities at low collision energies, the forward peak became dominant at the highest collision energy, 50 kJ/mol. The product kinetic energy distributions showed a good correlation with the initial collision energies, i.e., almost the same energy as the collision energy appeared as the product kinetic energy. These results suggested that the reaction proceeds via an intermediate complex, and the lifetime of the complex becomes shorter than its rotational period at high collision energy.

Crossed-beam velocity map imaging of collisional autoionization processes

Applying the velocity map imaging technique Penning ion formation as well as generation of associative ions is observed in autoionizing collisions of metastable neon atoms (Ne* 2p5 3s 3P2,0) with ground state argon targets in a crossed molecular beam experiment. Metastable neon reactants are obtained by nozzle expansion through a dc discharge ring. The quality of the obtained results clearly demonstrates the suitability of this new, particularly straightforward experimental approach with respect to angle and kinetic energy resolved investigations of Penning processes in crossed-beam studies which are known to provide the highest level of detail.

H abstraction dynamics by crossed-beam velocity map imaging: Cl+CH 3OH → CH 2OH+HCl

The crossed-beam reaction of ground state Cl ( 2 P 3/2) atoms with CH 3OH have been studied using the technique of velocity map imaging (VELMI). The hydroxymethyl (CH 2OH) radical was detected via single-photon ionization using 157 nm laser light. The full double-differential cross-sections were obtained at a collision energy of 8.7 kcal/mol. The angular distribution was predominantly in the sideways-backward direction with respect to the incoming alcohol beam, suggesting direct abstraction dynamics. The average translational energy release was 6.1 kcal/mol, out of 15.1 kcal/mol available. The technique of vacuum ultraviolet one-photon ionization in conjunction with VELMI promises to be useful for studying the reaction dynamics for many polyatomic systems.